Structure and method of Tinv scaling for high κ metal gate technology

ABSTRACT

A complementary metal oxide semiconductor (CMOS) structure including a scaled n-channel field effect transistor (nFET) and a scaled p-channel field transistor (pFET) which do not exhibit an increased threshold voltage and reduced mobility during operation is provided Such a structure is provided by forming a plasma nitrided, nFET threshold voltage adjusted high k gate dielectric layer portion within an nFET gate stack, and forming at least a pFET threshold voltage adjusted high k gate dielectric layer portion within a pFET gate stack. In some embodiments, the pFET threshold voltage adjusted high k gate dielectric layer portion in the pFET gate stack is also plasma nitrided. The plasma nitrided, nFET threshold voltage adjusted high k gate dielectric layer portion includes up to 15 atomic % N 2  and an nFET threshold voltage adjusted species located therein, while the plasma nitrided, pFET threshold voltage adjusted high k gate dielectric layer portion includes up to 15 atomic % N 2  and a pFET threshold voltage adjusted species located therein.

BACKGROUND

The present disclosure relates to a semiconductor structure and a methodof fabricating the same. More particularly, the present disclosureprovides a complementary metal oxide semiconductor (CMOS) structureincluding a scaled n-channel field effect transistor (nFET) and a scaledp-channel field transistor (pFET) which do not exhibit an increasedthreshold voltage and reduced mobility during operation. The presentdisclosure also provides methods of fabricating such a CMOS structure.

One trend in modern integrated circuit manufacture is to producesemiconductor devices, such as field effect transistors (FETs), whichare as small as possible. In a typical FET, a source and a drain areformed in an active region of a semiconductor substrate by implantingn-type or p-type impurities in the semiconductor material. Disposedbetween the source and the drain is a channel (or body) region. Disposedabove the body region is a gate electrode. The gate electrode and thebody are spaced apart by a gate dielectric layer.

Although the fabrication of smaller transistors allows more transistorsto be placed on a single substrate for the formation of relatively largecircuit systems in a relatively small die area, this downscaling canresult in a number of performance degrading effects. For example, thedownscaling of n-channel field effect transistors (nFETs) and p-channelfield effect transistors (pFETs) may result in a scaled inversion layerthickness (Tiny) being located between the gate dielectric layer and thesemiconductor substrate. The prior art scaled Tinv nFETs and pFETs,however, exhibit a shift in threshold voltage and a reduction inelectron/hole mobility which, in turn, negatively impact the performanceof the scaled Tinv nFET or pFET device.

SUMMARY

A complementary metal oxide semiconductor (CMOS) structure including ascaled n-channel field effect transistor (nFET) and a scaled p-channelfield transistor (pFET) which do not exhibit an increased thresholdvoltage and reduced mobility during operation is provided. Such astructure is provided by forming a plasma nitrided, nFET thresholdvoltage adjusted high k gate dielectric layer portion within an nFETgate stack, and forming at least a pFET threshold voltage adjusted highk gate dielectric layer portion within a pFET gate stack. In someembodiments, the pFET threshold voltage adjusted high k gate dielectriclayer portion in the pFET gate stack is also plasma nitrided. The plasmanitrided, nFET threshold voltage adjusted high k gate dielectric layerportion includes up to 15 atomic % N₂ and an nFET threshold voltageadjusted species located therein, while the plasma nitrided, pFETthreshold voltage adjusted high k gate dielectric layer portion includesup to 15 atomic % N₂ and a pFET threshold voltage adjusted specieslocated therein.

In one aspect of the present disclosure a method of fabricating acomplementary metal oxide semiconductor structure (CMOS) is provided.The method includes providing a plasma nitrided, nFET threshold voltageadjusted high k gate dielectric layer portion within an nFET deviceregion of a semiconductor structure and a plasma nitrided, pFETthreshold voltage adjusted high k gate dielectric layer portion within apFET device region of the semiconductor substrate. A gate electrodelayer can then be formed atop both the plasma nitrided, nFET thresholdvoltage adjusted high k gate dielectric layer portion and the plasmanitrided, pFET threshold voltage adjusted high k gate dielectric layerportion. Thereafter, an nFET gate stack can be formed in the nFET deviceregion and a pFET gate stack can be formed in the pFET device region,wherein the nFET gate stack includes, from bottom to top, the plasmanitrided, nFET threshold voltage adjusted high k gate dielectric layerportion and a first patterned portion of the gate electrode layer andthe pFET gate stack includes, from bottom to top, the plasma nitrided,pFET threshold voltage adjusted high k gate dielectric layer portion anda second patterned portion of the gate electrode layer.

In one embodiment of the present disclosure, the providing the plasmanitrided, nFET threshold voltage adjusted high k gate dielectric layerportion within the nFET device region of the semiconductor structure andthe plasma nitrided, pFET threshold voltage adjusted high k gatedielectric layer portion within the pFET device region of thesemiconductor substrate includes forming a high k gate dielectric layerwithin the nFET device region of the semiconductor substrate and thepFET device region of the semiconductor substrate. A patterned trilayermetal stack including at least a pFET threshold voltage adjustingmaterial layer is formed on a portion of the high k gate dielectricwithin the pFET device region, while leaving another portion of the highk gate dielectric within the nFET device region exposed. An nFETthreshold voltage adjusting material layer is formed in both deviceregions. Next, an anneal is performed that diffuses nFET thresholdvoltage adjusting species from the nFET threshold voltage adjustingmaterial layer into the underlying portion of the high k gate dielectriclayer in the nFET device region, while diffusing pFET threshold voltagespecies from the pFET threshold voltage adjusting material layer intothe underlying portion of the high k gate dielectric in the pFET deviceregion. The anneal thus forms an nFET threshold voltage adjusted high kgate dielectric layer portion and a pFET threshold voltage adjusted highk gate dielectric layer portion. The nFET threshold voltage adjustingmaterial layer and the patterned trilayer metal stack are then removedexposing both the nFET threshold voltage adjusted high k gate dielectriclayer portion and the pFET threshold voltage adjusted high k gatedielectric layer portion. The exposed nFET threshold voltage adjustedhigh k gate dielectric portion and the pFET threshold voltage adjustedhigh k gate dielectric layer portion are then subjected to plasmanitridation forming the plasma nitrided, nFET threshold voltage adjustedhigh k gate dielectric layer portion and the plasma nitrided, pFETthreshold voltage adjusted high k gate dielectric layer portion.

In another embodiment of the present disclosure, the providing theplasma nitrided, nFET threshold voltage adjusted high k gate dielectriclayer portion within the nFET device region of the semiconductorstructure and the plasma nitrided, pFET threshold voltage adjusted highk gate dielectric layer portion within the pFET device region of thesemiconductor substrate includes forming a high k gate dielectric layerwithin the nFET device region of the semiconductor substrate and thepFET device region of the semiconductor substrate. The high k gatedielectric layer is then subjected to plasma nitridation to form aplasma nitrided high k gate dielectric layer. A patterned trilayer metalstack including at least a pFET threshold voltage adjusting materiallayer is formed on a portion of the plasma nitrided high k gatedielectric within the pFET device region, while leaving another portionof the plasma nitrided high k gate dielectric within the nFET deviceregion exposed. An nFET threshold voltage adjusting material layer isformed in both device regions. Next, an anneal is performed thatdiffuses nFET threshold voltage adjusting species from the nFETthreshold voltage adjusting material layer into the underlying portionof the plasma nitrided high k gate dielectric layer in the nFET deviceregion, while diffusing pFET threshold voltage species from the pFETthreshold voltage adjusting material layer into the underlying portionof the plasma nitrided high k gate dielectric in the pFET device region.The anneal thus forms the plasma nitrided, nFET threshold voltageadjusted high k gate dielectric layer portion and the plasma nitrided,pFET threshold voltage adjusted high k gate dielectric layer portion.The nFET threshold voltage adjusting layer and the patterned trilayermetal stack are then removed exposing both the plasma nitrided, nFETthreshold voltage adjusted high k gate dielectric layer portion and theplasma nitrided, pFET threshold voltage adjusted high k gate dielectriclayer portion.

In another aspect of the present disclosure, a further method isprovided that includes providing a plasma nitrided, nFET thresholdvoltage adjusted high k gate dielectric layer portion within an nFETdevice region of a semiconductor structure and a pFET threshold voltageadjusted high k gate dielectric layer portion within a pFET deviceregion of the semiconductor substrate. A gate electrode layer can thenbe formed atop both the plasma nitrided, nFET threshold voltage adjustedhigh k gate dielectric layer portion and the pFET threshold voltageadjusted high k gate dielectric layer portion. Thereafter, an nFET gatestack can be formed in the nFET device region and a pFET gate stack canbe formed in the pFET device region, wherein the nFET gate stackincludes, from bottom to top, the plasma nitrided, nFET thresholdvoltage adjusted high k gate dielectric layer portion and a firstpatterned portion of the gate electrode layer and the pFET gate stackincludes, from bottom to top, the pFET threshold voltage adjusted high kgate dielectric layer portion and a second patterned portion of the gateelectrode layer.

In this aspect of the present disclosure, the providing the plasmanitrided, nFET threshold voltage adjusted high k gate dielectric layerportion within the nFET device region of the semiconductor structure andthe pFET threshold voltage adjusted high k gate dielectric layer portionwithin the pFET device region of the semiconductor substrate includesforming a high k gate dielectric layer within the nFET device region ofa semiconductor substrate and the pFET device region of thesemiconductor substrate. A patterned trilayer metal stack including atleast a pFET threshold voltage adjusting material layer is formed on aportion of the high k gate dielectric within the pFET device region,while leaving another portion of the high k gate dielectric within thenFET device region exposed. An nFET threshold voltage adjusting materiallayer is formed in both device regions. The nFET threshold voltageadjusting material layer is then subjected to plasma nitridation forminga plasma nitrided, nFET threshold voltage adjusting material layer.Next, an anneal is performed that diffuses nitrogen and nFET thresholdvoltage adjusting species from the plasma nitrided, nFET thresholdvoltage adjusting material layer into the underlying portion of the highk gate dielectric layer in the nFET device region, while diffusing pFETthreshold voltage species from the pFET threshold voltage adjustingmaterial layer into the underlying portion of the high k gate dielectricin the pFET device region. The anneal thus forms the plasma nitrided,nFET threshold voltage adjusted high k gate dielectric layer portion andthe pFET threshold voltage adjusted high k gate dielectric layerportion. The plasma nitrided nFET threshold voltage adjusting materiallayer and the patterned trilayer metal stack are then removed exposingboth the plasma nitrided, nFET threshold voltage adjusted high k gatedielectric layer portion and the pFET threshold voltage adjusted high kgate dielectric layer portion.

Another aspect of the present application relates to a complementarysemiconductor (CMOS) structure that can be formed. In one embodiment, aCMOS structure is provided that includes a semiconductor substratehaving an nFET device region and a pFET device. An nFET gate stack islocated in the nFET device region and a pFET gate stack is located inthe pFET device region. The nFET gate stack includes, from bottom totop, a plasma nitrided, nFET threshold voltage adjusted high k gatedielectric layer portion including up to 15 atomic % N₂, and a firstpatterned portion of a gate electrode layer. The pFET gate stackincludes, from bottom to top, a plasma nitrided, pFET threshold voltageadjusted high k gate dielectric layer portion including up to 15 atomic% N₂, and a second patterned portion of a gate electrode layer.

In another embodiment of the present disclosure a complementarysemiconductor (CMOS) structure is provided that includes a semiconductorsubstrate having an nFET device region and a pFET device; and an nFETgate stack located in the nFET device region and a pFET gate stacklocated in the pFET device region, wherein the nFET gate stack includes,from bottom to top, a plasma nitrided, nFET threshold voltage adjustedhigh k gate dielectric layer portion including up to 15 atomic % N₂, anda first patterned portion of a gate electrode layer, and a pFET gatestack includes, from bottom to top, a pFET threshold voltage adjustedhigh k gate dielectric layer portion, and a second patterned portion ofa gate electrode layer.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a pictorial representation (through a cross sectional view)illustrating an initial structure including a semiconductor substratehaving an nFET device region and a pFET device region, an optionalinterfacial layer located on an upper surface of the semiconductorsubstrate in both device regions, and a high k gate dielectric layerlocated on an upper surface of the optional interfacial layer that canbe employed in one embodiment of the present disclosure.

FIG. 2 is a pictorial representation (through a cross sectional view)illustrating the initial structure of FIG. 1 after forming a trilayermetal stack on an upper surface of the high k gate dielectric layer.

FIG. 3 is a pictorial representation (through a cross sectional view)illustrating the structure of FIG. 2 after removing a first portion ofthe trilayer metal stack from atop the nFET device region, while leavinga second portion of the trilayer metal stack atop the pFET deviceregion.

FIG. 4 is a pictorial representation (through a cross sectional view)illustrating the structure of FIG. 3 after forming an nFET thresholdvoltage adjusting material layer and an optional metallic material layeratop the exposed upper surfaces of the structure in both device regions.

FIG. 5 is a pictorial representation (through a cross sectional view)illustrating the structure of FIG. 4 after performing an annealing thatdrives nFET threshold voltage adjusting species from the nFET thresholdvoltage adjusting material layer into the underlying high k gatedielectric layer within the nFET device region and pFET thresholdvoltage adjusting species from a metal layer of the trilayer stack intothe underlying high k gate dielectric within the pFET device region.

FIG. 6 is a pictorial representation (through a cross sectional view)depicting the structure of FIG. 5 after removing metal structures andthe nFET threshold voltage adjusting material layer from both deviceregions.

FIG. 7 is a pictorial representation (through a cross sectional view)depicting the structure of FIG. 6 after performing plasma nitridation,followed by an optional oxygen-free anneal step.

FIG. 8 is a pictorial representation (through a cross sectional view)depicting the structure of FIG. 7 after forming a gate electrode layerwithin both device regions.

FIG. 9 is a pictorial representation (through a cross sectional view)depicting the structure of FIG. 8 after performing further CMOSprocessing steps.

FIG. 10 is a pictorial representation (through a cross sectional view)depicting the initial structure of FIG. 1 after performing a plasmanitridation process, without any anneal, in accordance with anotherembodiment of the present application; the plasma nitridation processconverts the high k gate dielectric layer of the initial structure intoa plasma nitrided high k gate dielectric layer.

FIG. 11 is a pictorial representation (through a cross sectional view)depicting the structure of FIG. 10 after forming a trilayer metal stackon an upper surface of the plasma nitrided high k gate dielectric layer.

FIG. 12 is a pictorial representation (through a cross sectional view)of the structure of FIG. 11 after removing a first portion of thetrilayer metal stack from atop the nFET device region, while leaving asecond portion of the trilayer metal stack atop the pFET device region.

FIG. 13 is a pictorial representation (through a cross sectional view)illustrating the structure of FIG. 12 after forming an nFET thresholdvoltage adjusting material layer and an optional metallic material layeratop the exposed upper surfaces of the structure in both device regions.

FIG. 14 is a pictorial representation (through a cross sectional view)illustrating the structure of FIG. 13 after performing an annealing thatdrives nFET threshold voltage adjusting species from the nFET thresholdvoltage adjusting material layer into the underlying plasma nitridedhigh k gate dielectric layer within the nFET device region and pFETthreshold voltage adjusting species from a metal layer of the trilayerstack into the underlying plasma nitrided high k gate dielectric withinthe pFET device region.

FIG. 15 is a pictorial representation (through a cross sectional view)depicting the structure of FIG. 14 after removing metal structures andthe nFET threshold voltage adjusting material layer from both deviceregions.

FIG. 16 is a pictorial representation (through a cross sectional view)depicting the structure of FIG. 5 after forming an nFET thresholdvoltage adjusting material layer atop the exposed upper surfaces of thestructure in both device regions in accordance with a further embodimentof the present application.

FIG. 17 is a pictorial representation (though a cross sectional view)depicting the structure of FIG. 16 after performing plasma nitridationand an oxygen-free anneal.

FIG. 18 is a pictorial representation (through a cross sectional view)depicting the structure of FIG. 17 after forming a metallic materiallayer atop the exposed upper surfaces of the structure in both deviceregions, and performing a drive in anneal.

FIG. 19 is a pictorial representation (through a cross sectional view)depicting the structure of FIG. 18 after removing metal structures andthe nFET threshold voltage adjusting material layer from both deviceregions.

FIG. 20 is a pictorial representation (through a cross sectional view)depicting the structure of FIG. 19 after forming a gate electrode layerwithin both device regions.

FIG. 21 is a pictorial representation (through a cross sectional view)depicting the structure of FIG. 20 after performing further CMOSprocessing steps.

DETAILED DESCRIPTION

The present disclosure, which provides a complementary metal oxidesemiconductor (CMOS) structure including a scaled n-channel field effecttransistor (nFET) and a scaled p-channel field transistor (pFET) whichdo not exhibit an increased threshold voltage and reduced mobilityduring operation, and methods of fabricating the same, will now bedescribed in greater detail by referring to the following discussion anddrawings that accompany the present application. It is noted that thedrawings of the present application are provided for illustrativepurposes only and, as such, the drawings are not drawn to scale.

In the following description, numerous specific details are set forth,such as particular structures, components, materials, dimensions,processing steps and techniques, in order to provide a thoroughunderstanding of the various embodiments of the present disclosure.However, it will be appreciated by one of ordinary skill in the art thatthe invention may be practiced without these specific details. In otherinstances, well-known structures or processing steps have not beendescribed in detail in order to avoid obscuring the various embodimentsof the present disclosure.

It will be understood that when an element as a layer, region orsubstrate is referred to as being “on” or “over” another element, it canbe directly on the other element or intervening elements may also bepresent. In contrast, when an element is referred to as being “directlyon” or “directly over” another element, there are no interveningelements present. It will also be understood that when an element isreferred to as being “connected” or “coupled” to another element, it canbe directly connected or coupled to the other element or interveningelements may be present. In contrast, when an element is referred to asbeing “directly connected” or “directly coupled” to another element,there are no intervening elements present.

Reference is now made to FIGS. 1-9 which are pictorial representations(through cross sectional views) illustrating the CMOS structure of thepresent disclosure during various stages of fabrication in accordancewith one embodiment of the present application. The method of thisembodiment includes providing the initial structure 10 shown in FIG. 1.The initial structure 10 shown in FIG. 1 includes a semiconductorsubstrate 12 having an nFET device region 14 and a pFET device region16, an optional interfacial layer 18 located on an upper surface of thesemiconductor substrate 12 in both device regions, and a high k gatedielectric layer 20 located on an upper surface of the optionalinterfacial layer 18. When the optional interfacial layer 18 is notpresent in the initial structure 10, the high k gate dielectric layer 20would be located on an upper surface of the semiconductor substrate 12in both device regions. It is noted that although one nFET device region14 and one pFET device region 16 are shown and illustrated, thesemiconductor substrate 12 may include a plurality of nFET deviceregions and a plurality of pFET device regions located therein.

The semiconductor substrate 12 illustrated in FIG. 1 can be comprised ofany semiconductor material including, but not limited to, Si, Ge, SiGe,SiC, SiGeC, GaAs, GaN, InAs, InP and all other III/V or II/VI compoundsemiconductors. Semiconductor substrate 12 may also comprise an organicsemiconductor or a layered semiconductor such as Si/SiGe, asilicon-on-insulator (SOI), a SiGe-on-insulator (SGOI) or agermanium-on-insulator (GOI). In some embodiments, the semiconductorsubstrate 12 is composed of a Si-containing semiconductor material,i.e., a semiconductor material that includes silicon. The semiconductorsubstrate 12 may be doped, undoped or contain doped and undoped regionstherein. The semiconductor substrate 12 may include a single crystalorientation or it may include at least two coplanar surface regions thathave different crystal orientations (the latter substrate is referred toin the art as a hybrid substrate). When a hybrid substrate is employed,an nFET is typically formed on a (100) crystal surface, while a pFET istypically formed on a (110) crystal plane. The hybrid substrate can beformed by techniques that are well known in the art. See, for example,U.S. Pat. No. 7,329,923, U.S. Publication No. 2005/0116290, dated Jun.2, 2005 and U.S. Pat. No. 7,023,055, the entire contents of each areincorporated herein by reference.

The semiconductor substrate 12 may also include a first doped (n- or p-)region, and a second doped (n- or p-) region. For clarity, the dopedregions are not specifically shown in any of the drawings of the presentapplication. The first doped region and the second doped regiontypically have different conductivities. These doped regions are knownas “wells” and they are formed utilizing conventional ion implantationprocesses. For example, the nFET device region 14 may include an n-well,while the pFET device region 16 may include a p-well. The dopingconcentrations with the various well regions may be the same ordifferent.

At least one isolation region 15 is then typically formed into thesemiconductor substrate 12. The at least one isolation region 15 may bea trench isolation region or a field oxide isolation region. The trenchisolation region is formed utilizing a conventional trench isolationprocess well known to those skilled in the art. For example,lithography, etching and filling of the trench with a trench dielectricmay be used in forming the trench isolation region. Optionally, a linermay be formed in the trench prior to trench fill, a densification stepmay be performed after the trench fill and a planarization process mayfollow the trench fill as well. The field oxide may be formed utilizinga so-called local oxidation of silicon process. Note that the at leastone isolation region 15 provides isolation between neighboring gateregions, typically required when the neighboring gates have oppositeconductivities, i.e., nFETs and pFETs.

After processing the semiconductor substrate 12, optional interfaciallayer 18 can be optionally formed on the surface of the semiconductorsubstrate 12. The optional interfacial layer 18 can be formed utilizinga conventional growing technique that is well known to those skilled inthe art including, for example, oxidation or oxynitridation. In someembodiments, the optional interfacial layer 18 is formed by a wetchemical oxidation process. When the substrate 12 is a Si-containingsemiconductor, the optional interfacial layer 18 can be comprised ofsilicon oxide, silicon oxynitride or a nitrided silicon oxide. When thesubstrate 12 is other than a Si-containing semiconductor, the optionalinterfacial layer 18 may comprise a semiconducting oxide, asemiconducting oxynitride or a nitrided semiconducting oxide. Thethickness of the optional interfacial layer 18 is typically from about0.5 nm to about 1.2 nm, with a thickness from about 0.8 nm to about 1 nmbeing more typical. The thickness, however, may be different afterprocessing at higher temperatures, which are usually required duringCMOS fabrication. The optional interfacial layer 18 typically has adielectric constant of less than 8.0.

High k gate dielectric layer 20 is then formed overlying thesemiconductor substrate 12. In one embodiment, and as shown, the high kgate dielectric layer 20 is formed directly on an upper surface of theoptional interfacial layer 18. In another embodiment, not shown, thehigh k gate dielectric layer 20 can be formed directly on an uppersurface of the semiconductor substrate 12. The high k gate dielectriclayer 20 employed includes any dielectric metal oxide having adielectric constant that is greater than the dielectric constant ofsilicon oxide, e.g., 3.9. Typically, the high k gate dielectric layer 20has a dielectric constant greater than 4.0, with a dielectric constantof greater than 8.0 being even more typical. Exemplary high k dielectricmaterials that can be used as the high k gate dielectric layer 20include, but are not limited to, HfO₂, ZrO₂, La₂O₃, Al₂O₃, TiO₂, SrTiO₃,LaAlO₃, Y₂O₃, HfO_(x)N_(y), ZrO_(x)N_(y), La₂O_(x)N_(y), Al₂O_(x)N_(y),TiO_(x)N_(y), SrTiO_(x)N_(y), LaAlO_(x)N_(y), Y₂O_(x)N_(y), a silicatethereof, and an alloy thereof. In one embodiment, a Hf-containing high kmaterial such as HfO₂ is employed as the high k gate dielectric layer20. Multilayered stacks of these high k materials can also be employedas the high k gate dielectric layer 20. Each value of x is independentlyfrom 0.5 to 3 and each value of y is independently from 0 to 2.

The thickness of the high k gate dielectric layer 20 may vary dependingon the technique used to form the same. Typically, however, the high kgate dielectric layer 20 has a thickness from 0.5 nm to 10 nm, with athickness from 1.0 nm to 5 nm being even more typical. The high k gatedielectric layer 20 employed may have an effective oxide thickness onthe order of, or less than, 1 nm.

The high k gate dielectric layer 20 can be formed by methods well knownin the art including, for example, chemical vapor deposition (CVD),physical vapor deposition (PVD), molecular beam deposition (MBD), pulsedlaser deposition (PLD), liquid source misted chemical deposition(LSMCD), atomic layer deposition (ALD), and other like depositionprocesses.

Referring now to FIG. 2, there is illustrated the structure of FIG. 1after forming a trilayer metal stack 22 on an upper surface of the highk gate dielectric layer 20 in both the device regions. The trilayermetal stack 22 includes, from bottom to top, a first metal nitride layer24, a metal layer 26 and a second metal nitride layer 28.

The first metal nitride layer 24 and the second metal nitride layer 28of the trilayer metal stack 22 may be comprised of the same or differentmetal nitrides. Illustrative metal nitrides that can be employed as thefirst metal nitride layer 24 and the second metal nitride layer 28include, but are not limited to, TiN, TaN, WN, and TiAlN. Combinationsof these metal nitrides can also be employed. In one embodiment of thepresent disclosure, the first metal nitride layer 24 and the secondmetal nitride layer 28 are both composed of TiN. The first metal nitridelayer 24 and the second metal nitride layer 28 can be formed utilizingthe same or different deposition method. Illustrative deposition methodsthat can be employed in forming the first metal nitride layer 24 and thesecond metal nitride layer 28 include, but are not limited to, chemicalvapor deposition (CVD), plasma enhanced chemical vapor deposition,sputtering, and physical vapor deposition (PVD). The thickness of thefirst metal nitride layer 24 of the trilayer metal stack 22 may varydepending on the type of metal nitride employed as well as thedeposition technique used in forming the same. Typically, the firstmetal nitride layer 24 has a thickness from 5 Å (angstroms) to 50 Å,with a thickness from 10 Å to 30 Å being more typical from the firstmetal nitride layer 24. The thickness of the second metal nitride layer28 of the trilayer metal stack 22 may vary depending on the type ofmetal nitride employed as well as the deposition technique used informing the same. Typically, the second metal nitride layer 28 has athickness from 0.5 nm to 5 nm, with a thickness from 0.1 nm to 3 nmbeing more typical from the second metal nitride layer 28.

As mentioned above, the trilayer metal stack 22 also includes a metallayer 26 sandwiched between the first metal nitride layer 24 and thesecond metal nitride layer 28. The metal layer 28 includes any pFETthreshold voltage adjusting material layer such as, for example, Ta, Ti,Al, and Ge. Combinations or multilayers of these metallic materials canalso be employed as the metal layer 26. In one embodiment of the presentdisclosure, Al can be employed as the metal layer 26. The metal layer 26can be formed utilizing a conventional deposition process including, butnot limited to, chemical vapor deposition (CVD), physical vapordeposition (PECVD), sputtering, plating and physical vapor deposition(PVD). The thickness of the metal layer 26 of the trilayer metal stack22 may vary depending on the metallic material employed as well as thetechnique used in forming the same. Typically, the metal layer 26 of thetrilayer metal stack 22 has a thickness from 2 Å to 50 Å, with athickness from 5 Å to 20 Å being more typical. Metal layer 26 can alsobe referred to herein as a pFET threshold voltage adjusting materiallayer.

Referring now to FIG. 3, there is illustrated the structure of FIG. 2after removing a first portion of the trilayer metal stack 22 from atopthe nFET device region 14, while leaving a second portion of thetrilayer metal stack atop the pFET device region 16. The remainingsecond portion of the trilayer metal stack 22, which can also bereferred to herein as a patterned trilayer metal stack, is labeled as22′ in the drawing. It is observed that the patterned trilayer metalstack 22′ is employed as a block mask so as to prevent subsequentdiffusion of an nFET threshold voltage adjusting species from an nFETthreshold voltage adjusting material layer (to be subsequently formed)into a portion of the high k gate dielectric layer 20 that is locatedwithin the pFET device region 16. Also, the patterned trilayer metalstack 22′ includes a pFET threshold voltage adjusting material as one orits layers as such, and during a subsequent anneal, this layer canstabilize the threshold voltage of the pFET device.

The structure shown in FIG. 3 is formed by lithography and etching. Thelithography step includes first providing a photoresist (not shown) atopthe upper surface of the trilayer metal stack 22. The photoresist caninclude a positive-tone photoresist material, a negative-tonephotoresist material or a hybrid photoresist material, each of which iswell known to those skilled in the art. The photoresist can be formedutilizing any conventional resist deposition process such as, forexample, spin-on coating, spray coating or evaporation. After applyingthe photoresist on an upper surface of the trilayer metal stack 22, thephotoresist is exposed to a desired pattern of radiation and thereafterthe exposed resist is developed utilizing a conventional resistdeveloper. This results in a patterned photoresist (not shown) atop thetrilayer metal stack 22 in the pFET device region 16. The exposedtrilayer metal stack 22 in the nFET device region 14 is then etchedutilizing dry etching, wet etching or a combination thereof. Dry etchingincludes reactive ion etching, plasma etching, ion beam etching or laserablation. Wet etching includes a chemical etchant that selectivelyremoves at least one of the layers of the trilayer metal stack 22 in thenFET device region 14. The patterned resist can be removed anytime afterthe pattern has been transferred into one of the layers of the trilayerstack 22 in the nFET device region 14 utilizing a conventional resistremoval process such as, for example, ashing. Alternatively, thepatterned resist can remaining atop the trilayer metal stack 22 in thepFET device region 16 during the removal of the exposed portions of thetrilayer metal stack 22 in the nFET device region 14 and be removedafter completely removal of the trilayer metal stack from the nFETdevice region 14 by a conventional resist removal process such as, forexample, ashing. The etching, which may include a single etch ormultiple etches, stops on an upper surface of the high k gate dielectriclayer 20. As such, a portion of the high k gate dielectric layer that iswithin the nFET device region 14 is now exposed.

Referring now to FIG. 4, there is shown the structure of FIG. 3 afterforming an nFET threshold voltage adjusting material layer 30 and anoptional metallic material layer 32 atop the exposed upper surfaces,e.g., the exposed high k gate dielectric layer 20 in the nFET deviceregion 14 and the patterned trilayer metal stack 22′ in the pFET deviceregion 16, of the structure in both device regions. It is also observedthat a portion of the nFET threshold voltage adjusting material layer 30is located on exposed sidewalls of the patterned trilayer metal stack22′.

The nFET threshold voltage adjusting material layer 30 can comprise arare earth metal-containing material or an alkaline earthmetal-containing material. The rare earth metal-containing materialsthat can be used as the nFET threshold voltage adjusting material layer30 include an oxide or nitride of at least one element from Group IIIBof the Periodic Table of Elements (CAS version) including, for example,La, Ce, Pr, Nd, Pm, Sm, Eu, Ga, Tb, Dy, Ho, Er, Tm, Yb, Lu or mixturesthereof. In one embodiment, lanthanum-containing compounds such as La₂O₃or LaN are employed as the nFET threshold voltage adjusting materiallayer 30.

The rare earth metal-containing material is formed utilizing aconventional deposition process including, for example, evaporation,molecular beam deposition, metalorgano chemical vapor deposition(MOCVD), atomic layer deposition (ALD), physical vapor deposition (PVD)and other like deposition processes. In one embodiment, the rare earthmetal-containing material is formed by placing the structure into theload-lock of a molecular beam deposition chamber, followed by pumpingthis chamber down to the range of 10⁻⁵ Torr to 10⁻⁸ Torr. After thesesteps, the structure is inserted, without breaking vacuum into thegrowth chamber where the rare earth metal-containing material such as Laoxide is deposited by directing atomic/molecular beams of the rare earthmetal and oxygen or nitrogen onto the structure's surface. Specifically,because of the low pressure of the chamber, the releasedatomic/molecular species are beamlike and are not scattered prior toarriving at the structure. A substrate temperature of about 300° C. isused. In the case of La₂O₃ deposition, the La evaporation cell is heldin the temperature range of 1400° C. to 1700° C., and a flow rate of 1sccm to 3 sccm of molecular oxygen is used. Alternatively, atomic orexcited oxygen may be used as well, and this can be created by passingthe oxygen through a radio frequency source excited in the range of 50Watts to 600 Watts. During the deposition, the pressure within thechamber can be in the range from 1×10⁻⁵ Torr to 8×10⁻⁵ Torr, and the Laoxide growth rate can be in the range from 0.1 nm per minute to 2 nm perminute, with a range from 0.5 nm per minute to 1.5 nm per minute beingmore typical.

The rare earth metal-containing materials that can be used as the nFETthreshold voltage adjusting material layer 30 comprises a compoundhaving the formula MA_(x) wherein M is an alkaline earth metal (Be, Mg,Ca, Sr, and/or Ba), A is one of O, S and a halide, and x is 1 or 2. Itis noted that the present disclosure contemplates alkaline earthmetal-containing compounds that include a mixture of alkaline earthmetals and/or a mixture of anions. Examples of alkaline earthmetal-containing compounds that can be used include, but are not limitedto, MgO, MgS, MgF₂, MgCl₂, MgBr₂, MgI₂, CaO, CaS, CaF₂, CaCl₂, CaBr₂,CaI₂, SrO, SrS, SrF₂, SrCl₂, SrBr₂, SrI₂, BaO, BaS, BaF₂, BaCl₂, BaBr₂,and BaI₂.

The alkaline earth metal-containing material can be formed utilizing aconventional deposition process including, for example, sputtering froma target, reactive sputtering of an alkaline earth metal under oxygenplasma conditions, electroplating, evaporation, molecular beamdeposition, MOCVD, ALD, PVD and other like deposition processes.

Notwithstanding the type of material used as the nFET threshold voltageadjusting material layer 30, the nFET threshold voltage adjustingmaterial layer 30 typically has a thickness from 0.1 nm to 5.0 nm, witha thickness from 0.3 nm to 2.0 nm being even more typical.

After providing the nFET threshold voltage adjusting material layer 30to the structure shown in FIG. 3, an optional metallic material layer 32can be formed atop the upper exposed surfaces of the nFET thresholdvoltage adjusting material layer 30. In some embodiments, the optionalmetallic material layer 32 is not formed. The optional metallic materiallayer 32, if present, includes a material that encapsulates the nFETthreshold voltage adjusting material layer 30 during a subsequent annealto prevent loss of material, e.g., nFET threshold voltage adjustingspecies, from the nFET threshold voltage adjusting material layer 30 andto ensure that the nFET threshold voltage adjusting species is driveninto the material of the high k gate dielectric layer 20 in the nFETdevice region 14.

The optional metallic material layer 32 can include a conductive metalnitride such as, for example, TiN, TaN, WN or combinations thereof. Inone embodiment, the optional metallic material layer 32 is composed ofTiN. The optional metallic material layer 32 can be formed utilizing anyconventional deposition process including, for example, chemical vapordeposition (CVD), plasma enhanced chemical vapor deposition (PECVD),sputtering or physical vapor deposition. The thickness of the optionalmetallic material layer 32 may vary depending on the type of materialemployed as well as the technique that is employed in forming the same.Typically, the optional metallic material layer 32 has a thickness from0.5 nm to 8 nm, with a thickness from 2 nm to 5 nm being more typical.

Referring to FIG. 5, there is depicted the structure of FIG. 4 afterperforming an annealing that drives nFET threshold voltage adjustingspecies (e.g., rare earth metal-containing ion or alkaline earthmetal-containing ion) from the nFET threshold voltage adjusting materiallayer 30 into the underlying high k gate dielectric layer 20 within nFETdevice region 14 and pFET threshold voltage adjusting species (e.g., anion of Ta, Ti, Al or Ge) from the metal layer 26 of the patternedtrilayer metal stack 22′ into the underlying high k gate dielectric 20within the pFET device region 16. In FIG. 5, reference numeral 34denotes an nFET adjusted high k gate dielectric layer portion thatincludes nFET threshold voltage adjusting species, while referencenumeral 36 denotes a pFET adjusted high k gate dielectric layer portionthat includes pFET threshold voltage adjusting species. In someembodiments, the nFET and/or the pFET threshold voltage species maydiffusion into portions of the underlying interfacial layer 18.

The ‘drive-in’ anneal used in forming the structure shown in FIG. 5 isperformed to induce diffusion of the threshold voltage adjusting speciesfrom the corresponding threshold voltage adjusting material layer, e.g.,layer 28 or 30, into the underlying portions of the high k gatedielectric layer 20. The temperature of the drive-in anneal is typicallyperformed at a temperature from 400° C. to 1100° C., with a temperaturefrom 700° C. to 1000° C. being more typical. The drive-in anneal may beperformed utilizing a furnace anneal, a rapid thermal anneal, a laseranneal or a microwave anneal. The duration of the drive-in anneal mayvary depending on the type of anneal employed. Typically, the durationof the drive-in anneal is from 1 second to 2 hours, with a duration from30 seconds to 0.5 hours being more typical.

Referring now to FIG. 6, there is shown the structure of FIG. 5 afterremoving metal structures, e.g., the optional metallic material layer 32and patterned trilayer metal stack 22′, and the nFET threshold voltageadjusting material layer 30 from both device regions selective to thenFET adjusted high k gate dielectric layer portion 34 and the pFETadjusted high k gate dielectric layer portion 36. The removal of themetal structures is performed utilizing one or more etching stepsincluding wet etching and/or dry etching. In one embodiment, one or morewet etching steps are employed in removing the metal structures fromatop the nFET adjusted high k gate dielectric layer portion 34 and thepFET adjusted high k gate dielectric layer portion 36.

Referring now to FIG. 7, there is illustrated the structure of FIG. 6after performing plasma nitridation, followed by an optional oxygen-freeanneal step. In FIG. 7, reference numeral 38 denotes the plasmanitrided, nFET adjusted high k gate dielectric layer portion andreference numeral 40 denotes the plasma nitrided, pFET adjusted high kgate dielectric layer portion.

The plasma nitridation can be performed utilizing any conventionalplasma nitridation tool. The plasma nitridation process can be performedusing any nitrogen-containing plasma source such as, for example, N₂,NH₃, N₂O and NO. The plasma nitridation is typically performed at atemperature from 0° C. to 500° C., with a plasma nitridation temperaturefrom 100° C. to 375° C. being more typical. In some embodiments, aspecial tool called a slot plate antenna (SP) tool is used to performthe plasma nitridation. In further embodiments, the plasma nitridationis performed using a two liter flow of nitrogen in which Ar is employedas the carrier gas.

Following the plasma nitridation process, an optional oxygen-free annealcan be performed. The oxygen-free anneal is performed in an ambient inwhich substantially no oxygen (less than 0.5 ppm) is present. In oneembodiment, the oxygen-free anneal is performed in an inert ambient suchas, for example, He, Ar, or mixtures thereof. The oxygen-free anneal istypically performed at a temperature from 400° C. to 800° C., with anoxygen-free anneal temperature from 650° C. to 750° C. being moretypical. The oxygen-free anneal may be performed utilizing a furnaceanneal, a rapid thermal anneal, a laser anneal or a microwave anneal.The duration of the oxygen-free anneal may vary depending on the type ofanneal employed. Typically, the duration of the oxygen-free anneal isfrom 1 second to 2 hours, with a duration from 60 seconds to 0.5 hoursbeing more typical.

The plasma nitrided, nFET adjusted high k gate dielectric layer portion38 and the plasma nitrided, pFET adjusted high k gate dielectric layerportion 40 each have a concentration of nitrogen therein that is up to15 atomic % N₂. Typically, the concentration of nitrogen in both theplasma nitrided, nFET adjusted high k gate dielectric layer portion 38and the plasma nitrided, pFET adjusted high k gate dielectric layerportion 40 is from 5 atomic % N₂ to 12 atomic % N₂.

Referring to FIG. 8, there is shown the structure of FIG. 7 afterforming a gate electrode layer 42 within both device regions. As shown,the gate electrode layer 42 is formed atop the plasma nitrided, nFETadjusted high k gate dielectric layer portion 38 and the plasmanitrided, pFET adjusted high k gate dielectric layer portion 40 of thestructure shown in FIG. 7.

The gate electrode layer 42 that is employed may comprise any conductivematerial including, but not limited to, polycrystalline silicon,polycrystalline silicon germanium, an elemental metal (e.g., tungsten,titanium, tantalum, aluminum, nickel, ruthenium, palladium andplatinum), an alloy of at least one elemental metal, an elemental metalnitride (e.g., tungsten nitride, aluminum nitride, and titaniumnitride), an elemental metal silicide (e.g., tungsten silicide, nickelsilicide, and titanium silicide) and multilayers thereof. In oneembodiment, the gate electrode layer 42 is comprised of elemental metal.In some instances, a single layer of conductive material is formed andis employed as the gate electrode layer 42. In other instances, a firstlayer of conductive material and a second layer of conductive materialare formed and are employed as the gate electrode layer 42. In oneembodiment, the gate electrode layer 42 may include a stack, from bottomto top, of a conductive metal layer and an upper conductiveSi-containing material layer; the conductive metal layer has a higherconductivity than the conductive Si-containing material layer.

The gate electrode layer 42 can be formed utilizing a conventionaldeposition process including, for example, chemical vapor deposition(CVD), plasma enhanced chemical vapor deposition (PECVD), evaporation,physical vapor deposition (PVD), sputtering, chemical solutiondeposition, atomic layer deposition (ALD) and other liked depositionprocesses. When Si-containing materials are used as the gate electrodelayer 42, the Si-containing materials can be doped within an appropriateimpurity by utilizing either an in-situ doping deposition process or byutilizing deposition, followed by a step such as ion implantation inwhich the appropriate impurity is introduced into the Si-containingmaterial. When a metal silicide is formed, a conventional silicidationprocess is employed.

The as deposited gate electrode layer 42 typically has a thickness from5 nm to 200 nm, with a thickness from 20 nm to 100 nm being moretypical. The conductive material employed as the gate electrode layer 42in the different device regions can be the same or different. Differentgate conductive materials can be formed using block mask technology.

In some embodiments, an optional hard mask material (not shown) can beformed atop the gate electrode layer 42. The optional hard mask materialincludes an oxide, a nitride, an oxynitride or any combination thereofincluding multilayered stacks. When present, the optional hard maskmaterial is formed utilizing a conventional deposition process wellknown to those skilled in the art including, for example, CVD and PECVD.Alternatively, the optional hard mask material can be formed by athermal process such as, for example, oxidation and/or nitridation. Thethickness of the optional hard mask material may vary depending on theexact hard mask material employed as well as the process that is used informing the same. Typically, the hard mask material has a thickness from5 nm to 200 nm, with a thickness from 10 nm to 50 nm being more typical.The hard mask material is typically employed when the conductivematerial is a Si-containing material such as polysilicon or SiGe.

Referring now to FIG. 9, there is depicted the structure of FIG. 8 afterperforming further CMOS processing steps including, for example,patterning the material stacks into patterned gate stacks 50, 52respectively, wherein patterned gate stack 50 is located within the nFETdevice region 14 and the patterned gate stack 52 is present in the pFETdevice region 16. The patterned gate stack 50 includes a patterned firstportion of the gate electrode layer 42′, a patterned portion of plasmanitrided, nFET adjusted high k gate dielectric layer portion 38′ and apatterned first portion of the optional interfacial layer 18′, whilepatterned gate stack 52 includes a patterned second portion of the gateelectrode layer 42″, a patterned portion of plasma nitrided, pFETadjusted high k gate dielectric layer portion 40′ and a patterned secondportion of the optional interfacial layer 18″. The patterning stepincludes the use of a conventional lithography (apply photoresistmaterial, exposed resist material to a desired pattern of radiation anddevelopment using a resist developer) and etching (wet etching, dryetching or a combination thereof) process.

The further CMOS processing also may include forming source/drainextension regions (not shown) within the semiconductor substrate 12 atthe footprint of each patterned gate stack. The source/drain extensionsregions can be formed utilizing any known extension ion implantationprocess. After the extension ion implantation, an anneal can be used toactivate the implanted extension ions. Next, optional sidewall spacer 54can be formed utilizing any known process including deposition of aspacer material, followed by etching. Typical spacer materials includean oxide and/or a nitride. After formation of the spacer, source/drainregions 56 can be formed into semiconductor substrate 12 at thefootprint of each patterned gate stack. The source/drain regions 56 canbe formed utilizing a source/drain ion implantation process followed byannealing.

In some embodiments, metal semiconductor alloy contacts can now beformed utilizing any process that is capable of forming a metalsemiconductor alloy atop a semiconductor material. In one embodiment,the metal semiconductor alloy contacts can be formed utilizing asilicide process. The silicide process can be self-aligned to the outeredge of the spacer. The silicide process includes forming a metalcapable of forming a metal semiconductor alloy when reacted with asemiconductor material. The metal used in forming the metalsemiconductor alloy contact can include, but is not limited to,tantalum, titanium, tungsten, ruthenium, cobalt, nickel, or any suitablecombination of those materials. A diffusion barrier such as titaniumnitride or tantalum nitride can be formed atop the metal. An anneal isperformed that causes reaction between the metal and the underlyingsemiconductor material forming metal semiconductor alloy regions.Typically, the anneal is performed at a temperature of at least 250° C.or above. A single anneal step or multiple anneal steps can be used. Anynon-reacted metal and the optional diffusion barrier are removed afterthe anneal has been performed. In some embodiments, a metalsemiconductor alloy contact can be formed directly atop the patternedconductive material, when no optional patterned hard mask is present andthe conductive material is composed of a Si-containing material.

Reference is now made to FIGS. 10-15 which are pictorial representations(through cross sectional views) illustrating the CMOS structure of thepresent disclosure during various stages of fabrication in accordancewith another embodiment of the present application. This embodiment ofthe present disclosure begins by first providing the initial structure10 shown in FIG. 1. As mentioned above, the initial structure 10 of FIG.1 includes a semiconductor substrate 12 having an nFET device region 14and a pFET device region 16, an optional interfacial layer 18 located onan upper surface of the semiconductor substrate in both device regions,and a high k gate dielectric layer 20 located on an upper surface of theoptional interfacial layer 18.

Referring now to FIG. 10, there is illustrated the initial structure ofFIG. 1 after performing a plasma nitridation process, without anyanneal. The plasma nitridation process performed at this stage convertsthe high k gate dielectric layer 20 of the initial structure into aplasma nitrided high k gate dielectric layer 60. The plasma nitridationprocess performed in this embodiment of the present disclosure includesthe conditions mentioned above for plasma nitridation in the firstembodiment of the present application. The plasma nitrided high k gatedielectric layer 60 that is formed has a concentration of nitrogen up to15 atomic %. Typically, the plasma nitrided high k gate dielectric layer60 that is formed has a concentration of nitrogen from 5 atomic % N₂ to12 atomic % N₂.

Referring now to FIG. 11, there is illustrated the structure of FIG. 10after forming a trilayer metal stack 22 on an upper surface of theplasma nitrided high k gate dielectric layer 60. The trilayer metalstack 22 includes, from bottom to top, a first metal nitride layer 24, ametal layer 26 and a second metal nitride layer 28. The trilayer metalstack 22 including the first metal nitride layer 24, the metal layer 26and the second metal nitride layer 28 is the same as that mentioned inthe embodiment described in FIGS. 1-9 above. As such, the trilayer metalstack 22 includes materials and is formed using the techniques mentionedabove in the embodiment described in FIGS. 1-9.

Referring to FIG. 12, there is illustrated the structure of FIG. 11after removing a first portion of the trilayer metal stack 22 from atopthe nFET device region 14, while leaving a second portion of thetrilayer metal stack 22 atop the pFET device region 16. The remainingsecond portion of the trilayer stack, which is also referred herein as apatterned trilayer metal stack, is a labeled as 22′ in the drawing. Thestructure shown in FIG. 12 is formed utilizing the same technique, i.e.,lithography and etching, as mentioned above in forming the structureshown in FIG. 3.

Referring to FIG. 13, there is illustrated the structure of FIG. 12after forming an nFET threshold voltage adjusting material layer 30 andan optional metallic material layer 32 atop the exposed upper surfacesof the structure in both device regions. The nFET threshold voltageadjusting material layer 30 and an optional metallic material layer 32in this embodiment are composed of materials, and are formed bytechniques as described above for the embodiment illustrated in FIGS.1-9.

Referring to FIG. 14, there is illustrated the structure of FIG. 13after performing an annealing that drives nFET threshold voltageadjusting species from the nFET threshold voltage adjusting materiallayer 30 into the underlying plasma nitrided high k gate dielectriclayer 60 within the nFET device 14 region and pFET threshold voltageadjusting species from metal layer 26 of the patterned trilayer stack22′ into the underlying plasma nitrided high k gate dielectric layer 60within the pFET device region 16. In FIG. 14, reference numeral 38denotes a plasma nitrided, nFET adjusted high k gate dielectric layerportion that includes nFET threshold voltage adjusting species, whilereference numeral 40 denotes a plasma nitrided, pFET adjusted high kgate dielectric layer portion that includes pFET threshold voltageadjusting species. In some embodiments, the nFET and/or the pFETthreshold voltage species may diffusion into portions of the underlyinginterfacial layer 18. The ‘drive-in’ anneal used in this embodiment ofthe present application includes the conditions mentioned above inregard to the drive-anneal used in forming the structure shown in FIG.5.

Referring to FIG. 15, there is illustrated the structure of FIG. 14after removing metal structures, e.g., the optional metallic materiallayer 32 and the patterned trilayer metal stack 22′, and the nFETthreshold voltage adjusting material layer 30 from both device regions.The removal of the metal structures is performed utilizing one or moreetching steps including wet etching and/or dry etching. In oneembodiment, one or more wet etching steps are employed in removing themetal structures from atop the plasma nitrided, nFET adjusted high kgate dielectric layer portion 38 and the plasma nitrided, pFET adjustedhigh k gate dielectric layer portion 40. The structure shown in FIG. 15can processed as shown in FIGS. 8-9 above.

Reference is now made to FIGS. 16-19 which are pictorial representations(through cross sectional views) illustrating the CMOS structure of thepresent disclosure during various stages of fabrication in accordancewith a further embodiment of the present application. The embodiment ofthe present disclosure begins by first providing the structure shown inFIG. 5.

Referring now to FIG. 16, there is illustrated the structure of FIG. 5after forming an nFET threshold voltage adjusting material layer 30 atopthe exposed upper surfaces of the structure in both device regions. Asshown, the nFET threshold voltage adjusting material layer 30 is locateddirectly on an upper surface of a portion of the high k gate dielectriclayer 20 in the nFET device region 14, and directly on the upper surfaceof the patterned trilayer stack 22′. The nFET threshold voltageadjusting material layer 30 includes one of the materials mentionedabove in the embodiment illustrated in FIGS. 1-9 and layer 30 can beformed as described above also.

Referring to FIG. 17, there is shown the structure of FIG. 16 afterperforming plasma nitridation and oxygen-free annealing. The plasmanitridation process introduces nitrogen into the nFET threshold voltageadjusting material layer 30 in both device regions; some nitrogen mayalso be introduced into the portion of the high k gate dielectric layer20 in the pFET region 16. The plasma nitridation is performed asdescribed above in the embodiment illustrated in FIGS. 1-9. Theoxygen-free annealing used in this embodiment includes the sameconditions as mentioned above for the oxygen-free annealing in theembodiment illustrated in FIGS. 1-11. In FIG. 17, reference numeral 75denotes the plasma nitrided nFET threshold voltage adjusting materiallayer that is formed in this step.

Referring to FIG. 18, there is illustrated the structure of FIG. 17after forming a metallic material layer 32 atop the exposed uppersurfaces of the structure in both device regions, and performing a drivein anneal. The metallic material layer 32 formed in this embodimentincludes one of the materials, and is formed using one of thetechniques, mentioned above for the optional metallic material layer 32used in the embodiment illustrated in FIGS. 1-9. The drive in annealincludes conditions mentioned above for the embodiment illustrated inFIGS. 1-9. In FIG. 18, reference numeral 38 denotes a plasma nitrided,nFET threshold voltage adjusted high k gate dielectric layer portion ofthe structure, while reference numeral 36 denotes the pFET thresholdvoltage adjusting high k gate dielectric layer portion of the structure.In this embodiment, the plasma nitrided, nFET threshold voltage adjustedhigh k gate dielectric layer portion 36 has a nitrogen concentration upto 15 atomic % N₂; the pFET threshold voltage adjusting high k gatedielectric layer portion does not typically include nitrogen since noneof the layers within the pFET device region 16 were subjected to plasmanitridation.

Referring to FIG. 19, there is illustrated the structure of FIG. 18after removing metal structures, e.g., the metallic material layer 32and the patterned trilayer metallic stack 22′, and the nFET thresholdvoltage adjusting material layer from both device regions. The removalof the metal structures and the nFET threshold voltage adjustingmaterial layer 30 from both device regions is the same as describedabove for removing those layers in the embodiment described in FIGS.1-9.

Referring to FIG. 20, there is illustrated the structure of FIG. 19after forming a gate electrode layer 42 within both device regions. Thegate electrode layer 42 used in this embodiment can include one of theconductive materials and can be formed using one of the techniquesmentioned above in forming the gate electrode layer 42 in the embodimentillustrated in FIGS. 1-9.

Referring to FIG. 21, there is illustrated the structure of FIG. 20after performing further CMOS processing steps including, for example,patterning the materials stacks into patterned gate stacks 90, 92respectively, wherein patterned gate stack 90 is located within the nFETdevice region 14 and the patterned gate stack 92 is present in the pFETdevice region 16. The patterned gate stack 90 includes a patterned firstportion of the gate electrode layer 42′, a patterned portion of plasmanitrided, nFET adjusted high k gate dielectric layer portion 38′ and apatterned first portion of the optional interfacial layer 18′, whilepatterned gate stack 92 includes a patterned second portion of the gateelectrode layer 42″, a patterned portion of pFET adjusted high k gatedielectric layer portion 40′ and a patterned second portion of theoptional interfacial layer 18″. The patterning step includes the use ofa conventional lithography (applying a photoresist material, exposedresist material to a desired pattern of radiation and development usinga resist developer) and etching (wet etching, dry etching or acombination thereof) process. The structure shown in FIG. 21 alsoincludes optional sidewall spacers 54 and source/drain regions 56 whichinclude materials and are formed as described above in the embodimentillustrated in FIGS. 1-9.

While the present disclosure has been particularly shown and describedwith respect to preferred embodiments thereof, it will be understood bythose skilled in the art that the foregoing and other changes in formsand details may be made without departing from the spirit and scope ofthe present invention. It is therefore intended that the presentdisclosure not be limited to the exact forms and details described andillustrated, but fall within the scope of the appended claims.

What is claimed is:
 1. A method of forming a complementary metal oxidesemiconductor comprising: providing a plasma nitrided, nFET thresholdvoltage adjusted high k gate dielectric layer portion within an nFETdevice region of a semiconductor structure and a plasma nitrided, pFETthreshold voltage adjusted high k gate dielectric layer portion within apFET device region of the semiconductor substrate, wherein saidproviding comprises: forming a high k gate dielectric layer within thenFET device region of the semiconductor substrate and the pFET deviceregion of the semiconductor substrate; forming a patterned trilayermetal stack including at least a pFET threshold voltage adjustingmaterial layer on a portion of the high k gate dielectric within thepFET device region, while leaving another portion of the high k gatedielectric within the nFET device region exposed; forming an nFETthreshold voltage adjusting material layer in both device regions;performing an anneal, wherein said anneal diffuses nFET thresholdvoltage adjusting species from the nFET threshold voltage adjustingmaterial layer into the underlying portion of the high k gate dielectriclayer in the nFET device region forming an nFET threshold voltageadjusted high k gate dielectric layer portion, while diffusing pFETthreshold voltage species from the pFET threshold voltage adjustingmaterial layer into the underlying portion of the high k gate dielectricin the pFET device region forming a pFET threshold voltage adjusted highk gate dielectric layer portion; removing the nFET threshold voltageadjusting material layer and the patterned trilayer metal stack exposingboth the nFET threshold voltage adjusted high k gate dielectric layerportion and the pFET threshold voltage adjusted high k gate dielectriclayer portion; and subjecting the exposed nFET threshold voltageadjusted high k gate dielectric portion and the pFET threshold voltageadjusted high k gate dielectric layer portion to plasma nitridationforming the plasma nitrided, nFET threshold voltage adjusted high k gatedielectric layer portion and the plasma nitrided, pFET threshold voltageadjusted high k gate dielectric layer portion; forming a gate electrodelayer atop both the plasma nitrided, nFET threshold voltage adjustedhigh k gate dielectric layer portion and the plasma nitrided, pFETthreshold voltage adjusted high k gate dielectric layer portion; andforming an nFET gate stack in the nFET device region and a pFET gatestack in the pFET device region, wherein the nFET gate stack includes,from bottom to top, the plasma nitrided, nFET threshold voltage adjustedhigh k gate dielectric layer portion and a first patterned portion ofthe gate electrode layer and the pFET gate stack includes, from bottomto top, the plasma nitrided, pFET threshold voltage adjusted high k gatedielectric layer portion and a second patterned portion of the gateelectrode layer.
 2. The method of claim 1 wherein the forming of thepatterned trilayer metal stack includes depositing on said high k gatedielectric a first metal nitride layer, said pFET threshold voltageadjusting material layer, and a second metal nitride layer, andpatterning said first metal nitride layer, said pFET threshold voltageadjusting material layer, and second metal nitride layer.
 3. The methodof claim 1 wherein the nFET threshold voltage adjusting material layerincludes a rare earth metal-containing material and an alkaline earthmetal-containing material, and said pFET threshold voltage adjustinglayer material is selected from Ta, Ti, Al and Ge.
 4. The method ofclaim 1 further comprising forming a metallic layer atop the nFETthreshold voltage adjusting material layer prior to performing saidanneal.
 5. The method of claim 1 wherein said anneal is performed at atemperature from 400° C. to 1100° C.
 6. The method of claim 1 whereinsaid plasma nitridation is performed at a temperature from 0° C. to 500°C.
 7. The method of claim 1 further comprising performing an oxygen-freeanneal in an ambient substantially absent of oxygen after said plasmanitridation, wherein said oxygen-free anneal is performed in an inertambient and at a temperature from 400° C. to 800° C.
 8. A method offorming a complementary metal oxide semiconductor comprising: providinga plasma nitrided, nFET threshold voltage adjusted high k gatedielectric layer portion within an nFET device region of a semiconductorstructure and a plasma nitrided, pFET threshold voltage adjusted high kgate dielectric layer portion within a pFET device region of thesemiconductor substrate: forming a high k gate dielectric layer withinthe nFET device region of the semiconductor substrate and the pFETdevice region of the semiconductor substrate; subjecting the high k gatedielectric layer to plasma nitridation to form a plasma nitrided high kgate dielectric layer; forming a patterned trilayer metal stackincluding at least a pFET threshold voltage adjusting material layer ona portion of the plasma nitrided high k gate dielectric within the pFETdevice region, while leaving another portion of the plasma nitrided highk gate dielectric within the nFET device region exposed; forming an nFETthreshold voltage adjusting material layer in both device regions;performing an anneal, wherein said anneal diffuses nFET thresholdvoltage adjusting species from the nFET threshold voltage adjustingmaterial layer into the underlying portion of the plasma nitrided high kgate dielectric layer in the nFET device region to form the plasmanitrided, nFET threshold voltage adjusted high k gate dielectric layerportion, while diffusing pFET threshold voltage species from the pFETthreshold voltage adjusting material layer into the underlying portionof the plasma nitrided high k gate dielectric in the pFET device regionto form the plasma nitrided, pFET threshold voltage adjusted high k gatedielectric layer portion; and removing the nFET threshold voltageadjusting material layer and the patterned trilayer metal stack exposingboth the plasma nitrided, nFET threshold voltage adjusted high k gatedielectric layer portion and the plasma nitrided, pFET threshold voltageadjusted high k gate dielectric layer portion; forming a gate electrodelayer atop both the plasma nitrided, nFET threshold voltage adjustedhigh k gate dielectric layer portion and the plasma nitrided, pFETthreshold voltage adjusted high k gate dielectric layer portion; andforming an nFET gate stack in the nFET device region and a pFET gatestack in the pFET device region, wherein the nFET gate stack includes,from bottom to top, the plasma nitrided, nFET threshold voltage adjustedhigh k gate dielectric layer portion and a first patterned portion ofthe gate electrode layer and the pFET gate stack includes, from bottomto top, the plasma nitrided, pFET threshold voltage adjusted high k gatedielectric layer portion and a second patterned portion of the gateelectrode layer.
 9. The method of claim 8 wherein the forming of thepatterned trilayer metal stack includes depositing on said high k gatedielectric a first metal nitride layer, said pFET threshold voltageadjusting material layer, and a second metal nitride layer, andpatterning said first metal nitride layer, said pFET threshold voltageadjusting material layer, and second metal nitride layer.
 10. The methodof claim 8 wherein the nFET threshold voltage adjusting material layerincludes a rare earth metal-containing material and an alkaline earthmetal-containing material, and said pFET threshold voltage adjustinglayer material is selected from Ta, Ti, Al and Ge.
 11. The method ofclaim 8 further comprising forming a metallic layer atop the nFETthreshold voltage adjusting material layer prior to performing saidanneal.
 12. The method of claim 8 wherein said anneal is performed at atemperature from 400° C. to 1100° C.
 13. The method of claim 1 whereinsaid plasma nitridation is performed at a temperature from 0° C. to 500°C. and no oxygen-free anneal step follows said plasma nitridation.
 14. Amethod of forming a complementary metal oxide semiconductor comprising:providing a plasma nitrided, nFET threshold voltage adjusted high k gatedielectric layer portion within an nFET device region of a semiconductorstructure and a plasma nitrided, pFET threshold voltage adjusted high kgate dielectric layer portion within a pFET device region of thesemiconductor substrate, wherein the plasma nitrided, nFET thresholdvoltage adjusted high k gate dielectric layer portion comprises a highgate dielectric material containing up to 15 atomic % nitrogen and annFET threshold voltage adjusting species therein, and the plasmanitrided, pFET threshold voltage adjusted high k gate dielectric layerportion comprises a high gate dielectric material containing up to 15atomic % nitrogen and a pFET threshold voltage adjusting speciestherein; forming a gate electrode layer atop both the plasma nitrided,nFET threshold voltage adjusted high k gate dielectric layer portion andthe plasma nitrided, pFET threshold voltage adjusted high k gatedielectric layer portion; and forming an nFET gate stack in the nFETdevice region and a pFET gate stack in the pFET device region, whereinthe nFET gate stack includes, from bottom to top, the plasma nitrided,nFET threshold voltage adjusted high k gate dielectric layer portion anda first patterned portion of the gate electrode layer and the pFET gatestack includes, from bottom to top, the plasma nitrided, pFET thresholdvoltage adjusted high k gate dielectric layer portion and a secondpatterned portion of the gate electrode layer.
 15. The method of claim14 wherein the providing the plasma nitrided, nFET threshold voltageadjusted high k gate dielectric layer portion within the nFET deviceregion of the semiconductor structure and the plasma nitrided, pFETthreshold voltage adjusted high k gate dielectric layer portion withinthe pFET device region of the semiconductor substrate includes: forminga high k gate dielectric layer within the nFET device region of thesemiconductor substrate and the pFET device region of the semiconductorsubstrate; subjecting the high k gate dielectric layer to plasmanitridation to form a plasma nitrided high k gate dielectric layer;forming a patterned trilayer metal stack including at least a pFETthreshold voltage adjusting material layer on a portion of the plasmanitrided high k gate dielectric within the pFET device region, whileleaving another portion of the plasma nitrided high k gate dielectricwithin the nFET device region exposed; forming an nFET threshold voltageadjusting material layer in both device regions; performing an anneal,wherein said anneal diffuses nFET threshold voltage adjusting speciesfrom the nFET threshold voltage adjusting material layer into theunderlying portion of the plasma nitrided high k gate dielectric layerin the nFET device region to form the plasma nitrided, nFET thresholdvoltage adjusted high k gate dielectric layer portion, while diffusingpFET threshold voltage species from the pFET threshold voltage adjustingmaterial layer into the underlying portion of the plasma nitrided high kgate dielectric in the pFET device region to form the plasma nitrided,pFET threshold voltage adjusted high k gate dielectric layer portion;and removing the nFET threshold voltage adjusting material layer and thepatterned trilayer metal stack exposing both the plasma nitrided, nFETthreshold voltage adjusted high k gate dielectric layer portion and theplasma nitrided, pFET threshold voltage adjusted high k gate dielectriclayer portion.
 16. The method of claim 14 wherein the providing theplasma nitrided, nFET threshold voltage adjusted high k gate dielectriclayer portion within the nFET device region of the semiconductorstructure and the plasma nitrided, pFET threshold voltage adjusted highk gate dielectric layer portion within the pFET device region of thesemiconductor substrate includes: forming a high k gate dielectric layerwithin the nFET device region of the semiconductor substrate and thepFET device region of the semiconductor substrate; forming a patternedtrilayer metal stack including at least a pFET threshold voltageadjusting material layer on a portion of the high k gate dielectricwithin the pFET device region, while leaving another portion of the highk gate dielectric within the nFET device region exposed; forming an nFETthreshold voltage adjusting material layer in both device regions;performing an anneal, wherein said anneal diffuses nFET thresholdvoltage adjusting species from the nFET threshold voltage adjustingmaterial layer into the underlying portion of the high k gate dielectriclayer in the nFET device region forming an nFET threshold voltageadjusted high k gate dielectric layer portion, while diffusing pFETthreshold voltage species from the pFET threshold voltage adjustingmaterial layer into the underlying portion of the high k gate dielectricin the pFET device region forming a pFET threshold voltage adjusted highk gate dielectric layer portion; removing the nFET threshold voltageadjusting material layer and the patterned trilayer metal stack exposingboth the nFET threshold voltage adjusted high k gate dielectric layerportion and the pFET threshold voltage adjusted high k gate dielectriclayer portion; and subjecting the exposed nFET threshold voltageadjusted high k gate dielectric portion and the pFET threshold voltageadjusted high k gate dielectric layer portion to plasma nitridationforming the plasma nitrided, nFET threshold voltage adjusted high k gatedielectric layer portion and the plasma nitrided, pFET threshold voltageadjusted high k gate dielectric layer portion.